Rubber composition and its production.



No Drawing.

, To all whom it may concem UNI D STATES PATENT oEEIcE. I

.J'ONAS w. YLswoETI-I, E EAsm ORANGE, NEW JERSEY, 'AssIGNoE. TO HALoeENPRODUCTS COMPANY, OF WEST oEANGE, NEW JERSEY, A oEPoEATIoN OF NEWJERSEY.

E BBEE. COMPOSITION Be it known that I, J ONAS W. AYLswoE'rH,

a. citizen of the United States, and a resident of East Orange, in thecounty of Essexand State of New Jersey, have invented cerwin new anduseful Improvements in Rubber Compositions and Their Production, ofwhich the following is a description.

My invention relates to new and im roved rubber compositions andprocesses 0 making the same.

My invention is based on my dlscovery that the chlorin or other euivalent substitution products of naphtha ene or their oxidized productsor derivatives facilitate the mixing and union of sulfur and rubber invulcanization and remain in the vulcanized rubber in the form of asolidified solution and contribute thereto certain unique and valuableproperties. The various .products formed vary over a wide range in theirproperties, depending upon the ingredients used, that is, upon thepercentage and kind of chloro-naphthalene, the quality and percentage ofrubber, the percentage of sulfur, and also, when a filling material isused, upon its amount and character. These com.- positions areespecially adapted for such purposes as the electrical insulationof'wires and cables, the electrical insulation and protection ofmetal-containers for batteries, for bakingjapan or lacquer, forchemically re-' sistant coatings for metals, and for forming variousarticles and products in whichrubber compositions are" used, as forexample,-

in golf balls. Orraccount of the strong adhesion of these compounds,they form good cementin materials for cementing together metal and otherarticles. The chloro-naphthalene constituents render the productsnon-inflammable or difficultly so, depending upon the ingredientscomposing the compo-- sition.

Hard rubber compositions can be made in accordance with myinventionwhich are much less. brittle than the correspondin compositions madewithout chloronaphtha ene constituents, and which are of great toughnessand strength and possess considerable flexibility. These compositions donot tend, to become brittle when-exposed to low temperatures, as is thecase with;

Specification of Letters Patent. 1 Application filed Aprnis,

-' to chemical agents.

Nnr'rs PRODUCTION.

Patented June 2, 1914. 1912. seria1N .s91,'72s. r

formspf hard rubber known prior to my invention. The ingredients may beso proportioned that a hard leathery sheet is obtained which isextremely strong, tough and durable,-,and is capable, of standing hightemperatures. much more readily than the ordinary known forms of hardrubber. This property adapts the material for packing purposes, gaskets,and the like, such as are used for steam or water pipes, andparticularlyfor pipes which carry active chemicals,

such as chlo'rin gas and the like. I The im-.

proved qualities of these compositions are due in art to the fact thatthe chloro naphtha enes dissolve sulfurperfectly in all proportions whenheated therewith, and also to the fact that the chloro-naphthalenesdissolve rubber in like manner, which greatly facilitates the union ofthe rubber and sul fur.- Some of the chloro-naphthalenes are toughwax-like substances, and these have high melting points and are veryresistant They are all insoluble 1n water and unaffected-by alkaline oracid solutions,'excepting very concentrated hot oxidizing acids, such asnitric, sulfuric and chromic. With the, exception ofmonochloro-naphthalene and mono-bromomaph thalene, which are oilyliquids that do not solidify except at very low temperatures, thehalogen naphthalenes are solids, some soft and waxAlike, others toughand flexible,

others hard and wax-like, andstill others.

hard like a fused mineral salt. All of these substances have smallcoefiicients of expansionb .heat'ias compared with ordinary vulcanlzedrubber and they contribute this p p t tions, w 'ch makes it possible toemploy these compositions for, coatings on metal which adhere and remainin, place through considerable temperature changes. Examples of comositions made in accordance with my invention are as. f ll v Unaphthalene, 01:0 100' terial, preferably non-fi rous; No. 2.100 partsof rubbelgfi to my improved rubber composi-.'

-No. 1. parts ofrubbenfi to 18 parts v of sulfur, 10 to 30 parts ofmono-chloroarts of filling 'ina- 100 of sulfur, to 100 parts of solidchloronaphthalene, preferably the tri-, tetra-, or

hexa-chloro-na-phthalenes or mixtures of the same.

' Semi-hard compositions.

' ents being either finely comminuted or added in the melted state, andthe resulting mixture or compound .then vulcanized in the usual manner.It is preferable, however, to

.mix the chloro-naphthalene constitutents positions.

ployed, they may be added to the mixture at before adding the sulfur,has sometimes-the high heat necessary in mixing some forms ofchloro-naphthalene will cause a premature vulcanization to take placeupon the mixing rolls ifthe sulfur is mixed first. Furthermore, itisadvisable to allow the mixture to cool somewhat before adding thesulfur. The chloro-naphthalene constituents appear to cause more rapidvulcanization than is the case with the same grades of rubber in whichthese constituents are not used. The qualities of all of thesecompositions,as well as of those described hereinafter, depend somewhatupon the natureof the rubber, as is the case in all rubber com- Wherefilling materials are emany convenient stage of the process prior tovulcanization, but preferably these materials are added after thesulfur. The mixture of ingredients should be thoroughly masticatedbefore vulcanization.

Wherever rubber is mentioned herein I mean either the pure rubber, orthe average mixtures of rubber used in the arts, such as mixtures ofPara, African and Guayule rubber.

The following is an example of a composition made in accordance with myinvention and suitable for baking japan and lacquer for coating metalsN0 4. 50 parts of Para rubber, 50 parts of Guayule rubber, parts ofsulfur, 25 to 200 parts solid chloro-naphthalene, 100 to 500 partsliquid mono-chloro-naphthalene.

In making this composition, the rubber and solid chloro-naphthaleneconstituents are first mixed on rolls and then the sulfur is added, andthe mixed compound is shredded and heated with the liquidmono-chloronaphthalene in which it dissolves, forming a varnish-likeliquid which thickens considerably on cooling. After complete solutionhas taken place, the solution may be used, preferably hot, as a dip forcoating objects, and it may also be applied with a brush or with an airbrush, or in any other suitable manner. Suitable pigments or fillingsubstances may be used in this composition. 1

After the articles are coated they are baked at a temperature varyingfrom 250 to 300 F. During the baking operation most of themono-ch]oronaphthalene is driven off, leaving a tough flexible film ofan improved rubber composition which adheres most tenaciously toobjects, including metals. Compositions made according to example No.4:are particularly adapted for coating wires and cables to insulate thesame, for coating other metal articles, such as metal batterycontainers, and for japanning or laqueiing articles. It is especiallyadapted for form ing an insulating and protective coating for the steelor nickel-plated steel storage battery containers of the-alkaline type,and in fact for coating metal articles of any kind where an insulatingchemically resistant coating or both is' desired.

The following is another example of a composition made in accordancewith my invention. This composition is adapted to be melted by heatingit and poured, as for example, into molds prior to vulcanizing, or to beused for dipping and coating, or impregnating articles or materials.

No. 5. 100 parts of rubber, 10 to 100 parts of sulfur, 150 to 550 partsof solid chloronaphthalene, preferably the tetra-, penta-, orhEa-chloro-naphthale'nes or mixtures of the machines. Form wound coilscoated and impregnated with this composition withstand the poundingto'which such coils are sub jected when they are driven into place inthe machine. In making c mpositions according to example No. 5, theingredients are mixed together and melted by heat, then poured intomolds or around the articles which are to be coated, and afterwardvulcanized. Where impregnation is desired,

any suitable method of impregnating the article or material with themolten composition may be employed, as for example, the

i if

well known vacuum and pressure method. The article or material isafterward subjected to a vulcanizing heat.

The following is an example of another baking japan or lacquer made inaccordance with my invention:

No. 6. Ingredients of the kinds and proportions given in examples Nos.1,2 or 3 are dissolved either separately or after mixing in a volatilesolvent which is of such a nature as to cause the rubber, sulfur andchloro-naphthalene to go into solution. An exampleof such a solvent isacetylene-tetrachlorid. The solution may be made in very concentratedform when heat is employed to assist in liquefaction. The solution maybe applied to the articles to be coated in any suitable way, as forexample, by dipping.

. The coated article is permitted to dry, and

is then subjected to'a vulcanizin heat, or the drying and vulcanizationmayv e accomplished as a continuous operation by suitably regulating theheat applied.

In my improved rubber compositions, the chloro-naphthalene constituentsemployed may be crude or pure products and the dis-.

tillation residues from crudechloro-naphthalenes may also be used. Otherhalogen substitution products of naphthalene, such as thebromo-naphthalenes, may be'used instead of the chloro=naphthalenes, butare more expensive. Instead of the halogen naphthalene, the oxidizedproducts or derivatives of halogenated naphthalenes, such as aredescribed in my prior application Sei rial No. 641,326, filed July 29,1911, may be employed in making my-improved rubber compositions insubstantially the same pro-- portlons as set forth above.

Other vulcanizing agents than sulfur may be used, such as pentasulfid ofantimony. The compositions made in accordance with examples 1,2, 4 and 5are particularly advantageous for the electrical insulation of wires andcables. Compositions made "in accordance with, examples 4 and 5 areparticularly advantageous for the electrical insulation of containersfor alkaline batteries,

and composition No. 3 is particularly adapted for making chemicallyresistant coatings for metals and for forming golf balls and otherproducts in which rubber compositions are used. A composition having thecharacteristics of the'hard leathery sheet hereinbefore described may bemade in accordance with example No. 3.

It will be understood that the phrases halogen derivative and chlorinderivative of naphthalene, in the claims, are intended to include theoxidized roducts or derivatives of the chlorin or ot er halogensubstitution products of naphthalene, which perform the functions andcontribute the propertiesvdescribed, as well as such substi-' tutionproducts themselves. Also that the phrases solution and dissolvedtogether include a solidified solution.

Having-now described my invention, what I claim as new therein anddesire to protect by Letters Patent is as follows 1. A composition ofmatter having com- 5 bined therein rubber, a halogen derivative 0naphthalene, and a vulcanizing agent, substantially as set forth.

2. A composition of matter having com- .bined therein rubber, a chlorinderivative of naphthalene, and a vulcanizing agent, substantially as setforth.

3. A composition of matter comprising a solution of vulcanized rubberand a halogen derivative of naphthalene, substantially as described.

4. A composition of matter having combined therein rubber, sulfur, and ahalo en substitution product of naphthalene, all dissolved together,substantially as described.

5. A composition of matter having combined therein rubber, a halogenderivative of naphthalene, and sulfur, substantially as set forth.

6. A composition of matter having com- 10, A composition ofmatter'having com-' bined therein rubber, a chlorin derivative ofnaphthalene, sulfur, and. filling material, substantially as set forth.

11. A composition of matter having com bined therein'a vulcanizable gum,a vulcanizing a ent, and a halogen derivative of naphtha ene, alldlssolved together, substantially as described.

1 12. A vulcanized rubber composition having combined therein a halogenderivative of naph alene, substantially as set forth.

13. A vulcanized rubber composition having combined therein a chlorinderivative of naphthalene, substantially as set forth. a

14. A vulcanized rubber composition having combined therein solid andliquid halogen derivatives of naphthalene, substan-v tially asdescribed.

15. Theprocess of making a' rubber composition,- which consists in.masticating a mixture of-rubber, a halogen derivative of naphthalene,and a vulcanizing agent and heating the resulting mixture to vulcanizethesame, substantially-as described.

16. The process of making a rubber composition, Which consists inmasticating rubber and a halogen derivative of naphthalene, masticatinga vulcanizing agent there cated mixture of rubber, a halogen deriva-ftive of naphthalene, a vulcanizing agent, and filling material, saidingredients being added in the order named, and heating the resultingmixture to vulcanize the same, substantially as described.

19. The method of making a rubber composition, Which consists inmasticating rubber and solid chloro-naphtha-lene, masticating sulfurtherewith, and heating the resulting mixture with a liquidchloro-naphthalene to dissolve the same, substantially as described.

20. The process of, making a'rubber compositioinwhich consists inmasticating rubber and a solid halogen derivative of naphthalene,masticating sulfur therewith, and heating the resulting mixture With aliquid halogen derivative of naphthalene to dissolve the same,substantially as described. 4'0

This specification signed and witnessed this 8th day of April, 1912'JONAS W. AYLSWORTH. Vitnesses:

HENRY LANAHAN, ANNA R. KLEHM.

